Hydrocarbon conversion



July 10, 1945.

RM Amma 2,380,010 HYDROC-ARBON 4CONVERSION Filed Dec. -1942 2 sheets-sheet 1 FIG.' 2

` ATToRNEYs.

my 10, 194s.

LIGHT GASES LIGHT GASES P. M. ARNOLD HYDROCARBON CONVERS ION 'Filed peo. 4, 1942 COOLERv 2 Sheets-Sheet 2 COOLER ATT ORNEYS.

`products,y from fractionations `Winkl bedevoted to the' isolation. of the desiredhydrocarbons. In accordance with assorto mzpitoimusolvr couvmtsroN f Philip M. Arnold, Bartlesville, okla., signor tof Phillips Petroleum Co Delaware mpany, a corporation of Appueauon December 4,1942, serial No. 467,870

4Claims.

fills invention relates .to a method whereby c talytic hydrocarbon conversions employing liquid or liquefied catalysts readily separable from the conversion reactioneilluents eitherby distillation or by two phase liquid separation, especially anhydrous hydrogen iluoride, can be conducted in a fractionating tower. 'I'hus the expense of contactors, reactors, etc., ordinarily employed in processes of this kind is eliminated.v

Moreparticularly the invention relates to a method whereby a hydrocarbon conversion can (Cl. Zen-683.4)

parafllns with aliphatic oleiins using liquid catalyst. Still another` object is to provide* an improved process of carrying out alkylation of isobutane with 4aliphatic: olens using liquid anhydrous hydrogen fluoride. Another object is to provide a process of the foregoing type wherein the conversion is carried out in a fractionatlng be eiected with a catalyst consisting of essentially anhydrous hydrogen fluoride in a fractionating tower. 'I'he invention'is particularly adaptable to alkylation` and isomerization of light hydrocarbons of the order of 3 to 6 carbon atoms per molecule, especially aliphatic hydrocarbons,

namely, paraiiins and olens. The invention is Aespecially applicable in the alkylation of lowl boiling isoparaiiins (C4 to Cs) with low-boiling.

aliphatic olens (C: to Cs) particularly isobutane with oleiins, especially isobutylene, andV also inl the isomerization of low-boiling parailins to the corresponding branched chain forms particularly normal butane to isobutane.

'I'he usual steps in carrying out hydrocarbon conversion reactions in liquid phase with a liquid Y. or liquefied catalyst'are (1) to contact the catalyst with the hydrocarbons to be converted under reaction conditions; (2) to separate the catalyst from the reaction eiliuents by fractionation if the eilluents are miscible with the catalyst or by setj tling steps and subsequent fractionation if the catalyst is not completely miscible with thereaction products, and (3) to recycle a portion of the catalyst to the reaction zone while the remaining. portion is being treated to revivify or concentrate the catalyst. Normally at least one fractionation step would be devoted to the recovery of the catalyst from the hydrocarbon eiiluent the reaction zone., Subsequent the present invention the fractionation step normaliye'xnployed rortheseparation of the catalyst froml the` conversiony zone leiiiueliigs is ,used as the reaction step as wellas for separating the ,"czata-A lyst from the reaction zone mixture. Thusfthe contactors,settlers, etc., ordinarily employed .prior ,to the catalyst separation step Vare eliminated.

The principalbbject ofthe present invention t ,is to provide an improved process of carrying out hydrocarbon conversions catalyzed with'liqid catalysts. Another object is to provide an improved proeess of carrying out alkylation of lsocolumn, thereby eliminating the amount oi expensive equipment required and simplifying the apparatus and control of the process.` Numerous other objects will hereinafter appear'.

The accompanying drawings portray ilve arrangements of apparatus that may advantageously be employed in carrying out the process of the presem-l invention. The several iigures will be exl plained in detail below. l

4In accordance with the present invention, a hydrocarbon conversion catalyzed with a liquid catalyst, whichmay be either normally gaseous and employed in the liqueed condition,l one which is normally liquid, or one which is normally solid and employed inthe liquid state, is

conducted by continuously feeding lthe hydrocarbons to be converted, at a single point or a plurality of points, into a iractionating column. y This column-is equipped withreboiling `means` at its bottom for reboiling the materiall approaching the bottom whereby -only the heavy components of the mixture are withdrawn as the bottom fraction. The column is so operated that simultaneous iractionation or rectification and the convertive1 reaction occur in the body'of the column. -Thel top "terlalnjqm'the column-takes p the same" mittens that at whlcnmaterlelfzis rea of the column is refluxedeither `by provisionofV a partial or total `condensing coilin'fassociatlon with the top of the column` or -by'recycling suitable liqueed components'of the overheadfvapors. A vaporous overhead iscontinuouslyjwithdrawn from the topv ofsthe columnand'this may consist essentially of light noncondensib1e-1gases 40` where total condensation 'was provided or lon a vaporized hydrocarbon, `1 orE of a' vvapo'rlzed' c'a'talyst, orof a mixtureoiahydroca on component or components and catalyst. 'Fromlthe bottom of the blumntnere is continuously withdrawn" a eavy reboiled fraction'-v lv'lhiclfif'inayor'may` not Inf/some I by-suitablePmeans hereinafter disclosed.' *Th withdrawal'ifoifmaplaceat'tessentilally finto they after? "steadyi statlperatioifs is established.` whereby a :balance 'isy vobtained-L'4 i ofcourse, the column is packed with the usual `means for insuring intimate contact between vapor and gas, such as trays or bubble plates. Raschig rings, etc.

The process outlined in the foregoing is especially applicable in the alkylation of isoparaiiins lwith low-boiling aliphatic oleiins. In such case separate a hydrocarbon-rich phase and a catalyst-rich phase, returning the hydrocarbon phase to the top of the column to serve as reflux, and also returning'a portion of the catalyst phase' to the column to serve as catalyst. Theheavy fraction removed as the bottom product consists es sentially of the alkylate product.

An especially preferred mode of effecting the alkylation of isobutane with oleflns using anhydrous HF as the catalyst involves feeding a stream containing the olefin, with or without a part of the isobutane. into the column at a plurality of vertically spaced points. Preferably isobutane is present in the olefin feed in amount only sufficient to replace that consumed in the alkylation. The tower, however, is so operated that the isobutane is in excess over the olen throughout 'the column. The amounts of the olefin stream fed into the column at each point are individually adjusted so that this excess of isobutane is maintained at each point in the column. Since the concentration of isobutane increases from the bottom to the top of the column, this means that relatively large amounts of the olefin are introduced at the higher of the several points, progressively decreasing as the column is descended. The make-up isobutane may be introduced in ad- -mixture with the. refluxed isobutane instead of in the olen feed, if desired. Or the make-up isobutane may be introduced lat any other point in the column'. Y f

In order that the invention will be more readily understood, it will first be described with respect to its application to the4 alkylation of isobutane with olefins using liquid anhydrous hydrogen fluoride as the catalyst. However, the invention may equally well be applied to the isomerization of normal butane, or other hydrocarbon. conver-l sion reactions. Figure 1 is a diagrammatic sketch of the invention as applied to the alkylation of isobutane with olefins. Referring toFig ure 1, olens such as propylene, butylenes, amylenes. etc., and isobutane in suitable proportions are introduced as feed to fractionator 4- through line I and branch lines 2, 3, etc. Infractionator 4 the feed is contacted with liquid anydrous hydrogen fluoride which is introducedr near the top of fractionator 4 through line I4.- The alkylate produced and admixed isobutane, oleiins, hydrophases, `the upper phase being rich in hydrocarbon and the lowerlayer or phase being rich in hydrogen'fluorlde. The hydrocarbon-,rich phase,

'which .is mostly isobutane, is returned to fractionator 4 as reflux by means of line I0. 'Ihe hydrogen uoride-rich phase is removed from accumulator 8 by means of line 9 to enter branched lines II and I2. The portion of the hydrogen fluoride entering line I2 is recycled to column 4 throughvline I4. A 'I'he portion of the hydrogen fluoride from line 9 entering branch line Il is removed from the system to an acid purification system (not shown) for the removal of any water,

acid soluble side reaction products, etc., that may version process or are included in the feed stream may accumulate in thesystem. To remove these non-condensible gases it kmay be necessary to draw a gas stream from the accumulator 8 through line I1.

In alkylation processes it is generally desirable f to supply an excess of the paraffin hydrocarbon,

in this case isobutane, in order to dilute the olefin and thus reduce side reactions such as po1ymer' ization, halogenation, decomposition, etc., of the` olefin.' Usually, it is desirable to maintain a given paraii'ln to olefin ratio. Consequently, fractionator 4 of Figure l is supplied with multiple feed points I, 2, 3, etc. Controls are provided for varying the rate of ow through these feed points. By means of` these controls the amountl of olefin to isobutane can be regulated to within a given ratio over a relatively large portion of the 40 fractionating column. At the top of the column gen uoride, etc., are reboiled by reboil arrange `ment I5 to effect the separation of these diluents from the alkylate which is the bottom product of fractionato'r 4. The alkylate is removed from the bottom of fractionator 4 through line I6. The unconverted hydrocarbons, consisting mostly of isobutane, separated from the alkylate pass up-` wardly through column 4 where they are again subjected to conversion conditions. The overhead product consisting essentially of isobutane and hydrogen nuoride leave tower 4 through line 5. condenser 6, and line I to enter accumulator 8. In accumulator 8 the liquened overhead product from fractionator 4 l separates into two liquid where the hydrogen fluoride and isobutane concentrations are high, a large amount of olefin canbe introduced. Lower down in the column, .where the concentration of isobutane is lower by reason of its consumption by the alkylation reaction and because' of the fraetionating effect of the tower, the controls can be set-to introduce smaller quantities of olen containing feed than at the top to maintain the isobutane-olefin ratio desired. It is to be noted that if the feed is an olefin-isobutane mixture, only enough isobutane introduced with the olefin feed to replace that consumed in the conversion reaction. The excess isobutane to maintain the desired paramn-olen ratio is continuously recycled to the fractionating column as 'reux. If the feed to the column does not conphase .in the reux accumulator is introduced into the column With the feed by means of line 2li. Thus in this case as in Figure 1, once the desired excess of paraiiin is charged to' the column 4, it is only necessary to supply enough isobutane .to replace that consumed by the conversion reaction or lost from the system. As in Figure 1, light hydrocarbons introduced with the feed or formed in the reaction are removed as gases from theA accumulator 8 via line I1. v

Y Figure 3 portrays a modification wherein a de# phlegmating type condenser 2| is used. In such an ,arrangement the overhead product is totally condensed and refluxed to the fractionafor, ex-

are In the operation of cept for light (non-condensible) gases which removed through line 22.

this modiication of the invention, the catalysty (anhydrous HF) and excess isobutane are kept in the fractionating tower and are not withdrawn therefrom. The required amount of isobutane to react with the oleflns is fed into the tower with the olens through lines I, 2, 3, etc. Dephlegmator 2| totally condenses the overhead product except for a small amount of light noncolumn is'shut down.

The foregoing lmodiiications have been described with respect to their application to the alkylation of'hydrocarbons using anhydrous hydrogen fluoride as the catalyst. The process may also -be employed to eiiect other types of hydrocarbon conversionV reactions using other liquid catalysts which may bemisci'ble or partially miscible with the hydrocarbons involved. VFor the case where the catalyst. is' less volatile than the hydrocarbons involved, a modiiication such as is shown in Figures 4 or 5 will be necessary. In this modification the hydrocarbons are removed overhead and, if desired, fractionated to. separate the unconverted hydrocarbons which may be reyturned to the reaction zone. If desired, multiple points of feed introduction with individual means for control may be used with modications such as shown in Figures 4 and 5 in order to permit introducing feed volumes in Aaccordance with catalyst concentration in the various` parts of'the column. The modification shown in Figure 44 is useful for catalysts of high boiling point that cannot be reboiled except at temperatures which might result in undesirable decomposition of the feed and reaction products. Line 53, pump 54,

and lines 5B and 59 are provided to recycle the -catalyst to the upper section of the column.

There must be a suicient number of trays above line '59 to reflux the catalyst and prevent it passing off overhead with the reaction products.

Examples of liquid catalysts which are less volatile than HF and which typify the catalysts contemplated in the preceding and in the suci ceeding paragraphs are: sulfuric acid, phosphoric acid, mixtures of sulfuric and phosphoric acids,

liquid addition compounds of boron fluoride and phosphoric acid, boron fluoride and lower aliphatic alcohols such as ethyl alcohol, boron uoride and lower fatty acids such as acetic acid, etc.

The apparatus of Figures 4 and 5 may also be used for processes wherein heavy hydrocarbons are decomposed to obtain lighter ones such as catalytic splitting (carbon-to-carbon scission).-

catalytic reconstruction (disproportionation) etc. In such processes the catalyst and heavy hydrocarbons are reboiled in the column and light reaction products are taken ofi overhead. Referringvto Figure 4, the heavy hydrocarbon feed to be converted by decomposition is charged as before to column 4 through line I and branch lines 2, 3, etc. In column 4 the heavy hydrocarbon is contacted with a catalyst introduced through lines 58 and 59. Sincethe boiling point of the catalyst may be considerably higher than the deposed of. Fresh or reviviiied catalyst is introduced'through `line 58. The reaction products consisting of light hydrocarbons are drawn off overhead through line 5, cooler 6, and pass through line 'I to accumulator 8. A portion of the liquid from accumulator 8 is returned to the column through lin'e 60, pump 6| and line $2 as liquid reiiux. The remaining portion is drawn off as the product through line 63 to further processing, storage, etc. Reboiler 55 is provided in the bottom of column 4 to effect reboiling of the kettle contents. 1

The apparatus of Figure 5 is similar to that shown in Figure 4 except that the catalyst is not recirculated by pumping. In this case the catalyst should be sufliciently volatile to permit re- -boiling and thus causing some of it to ascend as i be used is the polymerization of propylene to form hexylene using titanium tetrachloride as a catalyst. However this is only an example and is not intended to limit the possibilities for this operation.. The selection of a liquid catalyst meeting the requirements for this type of oper-'- ation will be Well within the skill of the art -in the light of this specification.

In instances where compounds, which have about the same volatility characteristics as the reactants and catalyst, but which are not reactive under the conditions in the fractionationreaction zone, are produced in or fed to the reaction zone there will be a tendency for such products to accumulate in the reaction zone. For example, in the case of alkylation of isobutane with olens using anhydrous hydrogen iluoride as the catalyst, if there i's 'any' normal butane present in the isobutane-olen feed it will tend\ to accumulate in the fractionator-reaction zone.

Normal butane is relatively inactive so 'farv as alkylation with oleflns in\ the presence of hydrofluoric acid as a catalystis concerned. Consequently, it is not consumed in the reaction to produce products of different characteristics as is isobutane. This results in the Vnormal butane being recycled with the excess isobutane in the fractionator-reactor, but since it is not consumed it steadily accumulates. No provision is indicated on the drawings for overcoming such a difiiculty. However, this diculty can be overcome byallowing the normal butane or other similar unreactive product to accumulate to some predetermined level and withdrawing it either as a side stram from the fractionating columnV or.

alkyiaung schuim with low-boiling aliphatic olens employing liquid anysuch manner as to maintain an excess of isobutane over olefin throughout the columnl simultaneously iractionating the mixture and eiecting catalytic alkylation of the isoparafn with the olefin in said column, reboiling the mixture approaching th`e bottom of said column and there- 'f by effecting separation of isobutae, olefin and hydrogen iluoride from the alkylate, continuously withdrawing from the bottom of said column a heavy fraction consisting essentially of a1- kylate, continuously withdrawing from the top of said column an overhead fraction consisting essentially otisobutane and hydrogen fluoride. condensing said overhead, effecting separation of the condensate into a liquid hydrocarbon phase comprising chiey isobutane and a hydrogen fluoride phase, returning all of said liquid hydrocarbon phase to the top of said column as reflux therefor, and returning at least a part of said hydrogen fluoride 'phase to said column to furnish catalyst for said alkylation.

2. The process of alkylating isoparaiins with aliphatic olens with an alkylating catalyst consisting essentially of liquid anhydrous hydrogen fluoride which comprises continuously'feeding a' stream of the isoparafiin and the olen into the upper portion of a fractionating column equipped with reboiling means, said stream containing isoparaflin in amount just sulicient to replace that consumed in the alkylation taking place in -the column, maintaining isoparain in excess over olefin throughout the column, maintaining. liquid anhydrous hydrogen 'fluoride in the column in amount suillcient'to catalyze the alkylation, simultaneously fractionating the mixture and effecting catalytic alkylation of the isoparaiiin with the olen in said column, reboiling the mixlighter materials including isoparaiiin, olefin and l catalyst, condensing all isoparain attaining the top of the column and returning all of the con- .densed'isoparafn to ,the top of the column as reflux therefor, and withdrawing from the bot- 3. The process of alkylating isoparamns with low-boiling aliphatic cleans with en aikylauon 'ture approaching the bottom of said column and I thereby freeing the alkylate bottom product from tom of said column a heavy fraction consisting i essentially of the alkylate formed therein.

catalyst consisting essentially of liquid anhydrous hydrogen fluoride which comprises continuously feeding a stream comprising the olefin into the upper portion of a fractionating column equipped with reboiling means, introducing said stream at a plurality of vertically spaced points in the upper portion of said column, including in said stream isoparamn in amount just suicient to replace that consumed in the alkylation reaction, maintainingan excess of isoparaflin over olefin throughout the column, individually adjusting the amount-of said olefin fed into said column at each of said vertically spaced points insuch manner as to maintain an excess of isoparaflln over olen throughout the column', reboiling the mixture approaching the bottom of said column and thereby effecting separation of isoparaiiin, olefin and hydrogen fluoride from the alkylate, continuously withdrawing from the bottom of said column a heavy fraction consisting essentially 'of the alkylate, and totally condensing the overhead product attaining the top of said column except for light non-condensible gases, andrefluxing the column with the entire condensate.

4. The process of alkylating isoparafiins with aliphatic olens with a. catalyst consisting essentially of liquid anhydrous hydrogen uoride which comprises continuously passing a stream of the isoparailn and'theplefin into the upper portion of a fractionating column equipped with reboiling means, said stream containing isoparaflin in amount just suflcient to replace that consumed in the alkylation taking place in the column, simultaneously feeding a stream of said catalyst into the upper portion of said column, maintaining isoparain in excess over` olefin `throughout the column, simultaneously fractionating the mixture and eiecting .catalyic alkylation of the isoparailn with the olen in said column,- reboiling the mixture approaching the bottom of said column and thereby freeing the alkylate bottom product from lighter materials including isoparaln, olen and catalyst, continu'- ously withdrawing a vaporous overhead consisting essentially of isoparaflinand'catalyst from the top yof said column, condensing said overhead, treating the resulting condensate to separately recover an isoparai-linic phase and a liquid catalyst phase, returning all of said isoparafilnic phase to the topof said column as reflux therefor, recycling at least a portion of saidv catalyst phase to said column, and withdrawing from the bottom of Asaid column a heavy fraction consisting essentially of the alkylate formed therein.

PHILIP M. ARNOLD. 

